Reaction product of an amine salt of an alkyl-dithio-carbonic acid with benzothiazyl chlorothiocarbonate and process of producing the same



Patented Oct. 4, 1932 UNITED' STAT-ES PATENT OFFICE WILLIAM B. TER HORST, OF NITRO, WEST VIRGINIA, ASSIGNOR TO THE RUBBER SERVICE LABORATORIES CO., OF AKRON, OHIO, A CORPORATION OF OHIO REACTION PRODUCT OF AN 'AMINE SALT OF AN ALKYL-DITHIO-CARBONIC ACID WITH BENZOTHIAZYL CHLOROTHIOCARBONATE AND PROCESS OF PRODUCING THE SAME No Drawing. Original application filed August 4,1927, Serial No. 210,712. Divided and. this application filed June 23, 1928.

The present invention relates to the manufacture of' vulcanization accelerators com: prising particularly those compounds obtained by combining the carbon disulfid derivatives of primary and secondary amines with the products obtained by reacting a mercaptothiazole and a chlorine derivative of carbon disulfid, sulfur or sulfur dioxide. The manufacture of the preferred class of accelerating compounds will 'be readilyunderstood from the following description and examples.

Certain mercapto-aryl-thiazole compounds, such as mercapto-benzo-thiazole, and metallic salts thereof, and its disulfid, heretofore have been described as providing a class of vulcanization accelerators capable of imparting certain desirable properties to a rubber mix and furthermore capable of producing such a product in a relatively short vulcanization period. 'It has now been found that a rubber product possessing greatly enhanced properties results after an equally short vulcanization period by replacing mercapto-benzo-thiazole or its known derivatives with certain reaction products thereof of a type hereinafter set forth.

The amine salts of alkyl-dithiocarbamic acids, as are well known, are produced by the action of carbon disulfid on primary and secondary aliphatic amines. It has now been found that such salts can be combined with the products obtained by reacting mercapto-thiazoles with the chlorine derivatives of carbon disulfid, of sulfur or of sulfur dioxide to produce stable compounds. Such compounds have been found to be active as accelerators of vulcanization when employed in a rubber mix and produce rubber products in a short period of time that possess high tensile strengths and other highly desirable characteristics advantageous in commercial products. 7

The mercapto thiazole products employed 7: inthe manner hereinafter set forth for the manufacture of the products desired are obtained preferably by reacting a metallic salt of a mercapto aryl thiazole with a chlorine V derivative of carbon disulfid, sulfur or sulfur dioxide. In the case of sodium mercapto- Serial .No. 287,897.

benzo thiazo1e and thiophosgene, the reaction most probably takes place in'the following manner: 7

Such a product may be designated as benzo thiazyl chlorthioca-rbonate. This reaction product and'other similarproducts have been combined with dithiocarbamates" in the manner set forth in the examples hereinafter de-- scribed in detailto produce reactionprodnets of the type and for the purpose desired. i

The compounds of the type comprising the subject-matter of the present invention are preferably manufactured according to the following example, although other modes of reacting the ingredients set forth, as well as and of a reaction product of'substantially equimolecular proportions of thiophosgene. and sodiinn mercapto-benzo thiazole having the probable formula of i were added to a quantity of hot benzol or other suitable solvent material, preferably anhydrous, and the mass maintained at a temperature of approximately60 to 7 0 C. for a period of timesuficient to permit the reaction to be'completed. From'four'tosix hours heating were sufficient for the temperature conditions given, but a longer or shorter period is necessary at lower or higher temperatures respectively. Thiophosgene and other analogous reaction products of mercapto compounds, manufactured by the reaction of loo other than equi-molecular proportions of the respective compounds have been reacted in. a like manner with carbon disulfid derivatives of the amines. i

As the reaction hereinbefore described proceeds, 'piperidine hydrochloride precipitates out while the reaction product desired remains in solutionin the. solvent employed.

' In order to permit 'all the pip-eridine hydrochloride to precipitate, it was found desirable, after the'reaction had been completed,

to allow the mass to-cool down and standundisturbed for some time. Thereupon the mass was-filtered and the filtrate, containing the desired reaction product, was evaporated nearly to dryness. The remaining portion of solvent was then removed, preferably by vacuum drying. The'residual brown mass comprising the product desired, is soluble in chloroform and other solvents.

The reaction product described has also been obtained by agitating and heating to- V gether the amine salt of an alkyl-dithiocarbamic acid with a substantially equal weight or. other proportion of'the thiophosgene reaction product of sodium mercapto-benzot'hiazole. Other similarly constituted'products can likewisebe prepared. Thus, the carbon'disulfid reaction product of ethyl- I amine, diethylamine, propylamine, butylamine having the formulae respectively of and other aliphatic primary and secondary amines can be used in place of piperidine mentioned in the example set forth. These c carbon disulfid derivatives of the amines can also be combined in other than equal proportions by weight with the thiophosgene, the per-chlor-methyl-mercaptan- '(CSCLQ, the sulfur chloride and other chlor sulfur compounds, as wellas with the methylene-chloride, and like reaction products of mercaptobenzo-thiazole, its metallic salts, particularly its sodium salt, and of similar derivatives of other mercapto-aryl-thiazole, thiophenol and di-mercaptans such {as the mercapto derivatives of penthiophene.

This case is a division of U. S. Patent No.

, thiaaolevderivative comprising vtreating piperidine-pentamethylene di thiocarbamate with benzo thiazyl chlorthiocarbonate.

4C. The process of preparing a mercapto thiazole derivative comprising the reaction between substantially equal weights of piperidine pentamethylene dithiocarbamate and of benzo thiazyl chlorthiocarbonate.

e 5. As a new product the mercaptothia'zole' derivative prepared by treating the amine salt of an alkyl-dithiocarbamic acid with benzothiazyl chlorthiocarbonate.

' 6. As a new product the mercapto thiazole derivative prepared by treating the piperidine "salt of an alkyl-dithiocarbamicacid with benzo 'thiazyl chlorthiocarbonate.

7. As a new product the mercapto thiazole derivative prepared by treating piperidinepentamethylene-dithiocarbamate with benzo thiazyl chlorthiocarbonate.- v v .8; As a new product the mercapto thiazole derivative preparedbythe reaction between substantially equal weights of piperidinepentamethylene-dithiocarbamate and of ben- Z o thiazyl chlorthiocarbonate. p

In'testimony whereof I hereunto aflix my signature. WILLIAM P. TER HORST, 

